Flour product and method for the preparation thereof



Patented June 15, 1948 UNITED G FFICE I FLOUR PRODUCT AND METHOD"FORTH"EPREPARATION THEREOF Jordan V. Bauer,:Elmwod Bark, Ill =.,.ass igmor,-;byniesne assignments, 1 to Stein, Hall & Coal-Inc. a. .corporat'ionof N ewYork No Drawing. Application April fifl, 1943,. Serial No. 485.204

Ii'jClaims. 1

This invention relates to anew andimproved flour product and a new andimproved. method for the preparation. thereof.

This application is a continuationeinepart. of Serial No. 400,147.,filedJ-uneZ'Z, 19.4 1, now.aban-- cloned.

Commercial flours of the types derived from cereal grains are known tohave many disadvantages for industrial uses,. as compared withrelatively pure starches. These disadvantages result largely from thefact that .flours contain not. only starch but also protein. This isespecially true of certain types ofv flours such .as, forv example,wheat and. rye flours. The presence of the protein modifies thecharacteristics. of the flours as a whole and, among. other things,inter.- feres with the dispersibility of the flours in water; Thus,ordinary flour, instead of dispersing to a' slurry as does starch, tendsto form doughly lumps which are verydiflicult. to disperse. Also, whensubjected to agitation. or. abeating. action whole flours foamexcessively, andltherefore cannot be used satisfactorily. in industrial;processes where any great amountof' agitation ispresent. For. thesereasons flours have. not heretofore presented very promisingpossibilities. for industrial usages.

One of, the objectsoi this. invention. is .to. provide a new andimprovedtype ofjfiour product which is free from the disadvantages aboveenumerated.

Another object of the inventionisto provide a. new and improved methodfor producing a flour product of.v the type described.

A, more specific object of the invention'isto.

providea new andimproved type of'fiour productwhichwill'disperse inwater to form arel'atively thin slurry without lumping up 01 forming. adough.

Still another specific object. of the. invention isto provide a new andimproved type of'flour. product which can be subjectedtoagitation inindustrial usageswithout excessive foaming,

Another objectof theinvention'is to: provide anew andimprovedtypeoffiour product which is.v relatively stable.

Inaccordance with the invention, these objects areaccomplished. bytreating cereal flourswith 2. formaldehyde undersubstantially dryconditions; orin. the presence of insuifi'cient moisture to form adough. The. expression "a formaldehyde is employed herein tocoverformaldehyde. and com-' pounds or compositions whichlib'eraterformaldehyde... e. g., paraformaldehyde, formaldehydegas; andcommercial solutions of formaldehyde; It: is

important for the. purpose oflthev invention, however,that-theformaldehydebe used insuch form thatlitmaybe intimatelydispersed with the. discrete. particlesoi the. flour. .Paraformaldehydein powder form: is- ,capableof such intimate dispersion. and -.is. verysuitable for this .purp'ose. Gaseous iormaldehyde i'sreadily absorbed bythe hour and. may be. introduced. by any of the well known. methods. oftreatingldry. pulverulent materials withgaseous. chemicals. The same istrue-with. commercial..,liqui'dIformaldehyde which, if. .used,.is.preferably, introduced as. a fine spray, so that. it.v canbedisseminat'ed 'athroug-hthe. flour and. not; cause. the. formationofdoughy particles due-.toilarge. localconcent ration's of moisture.Another. method. of. intro ducing. formaldehyde, in aqueoussolution'form is to disperse it in. a portion of dry pulverulentmaterial suchas' owdeified starchnor clay which. may. subsequently beblended. with.,the flour .Land. liberates .fo'rmaldehyde insitu.

Thetreatment of the. flour. maybe efiected. at' ordinary. temperatures.say. F.,- or at elevated temperatures. It. ordinary. temperatures areenip1oyed',... the percentage of. the. formaldehyd'e.ccmpound requiredis. somewhat greater. than that required, at elevated temperatures.Thu-8;. with ordinary. or. relativelylowtemperature. conditions as.little as. .0'.'1T%l has been. found to- .be' efictive; while. withelevated tempera'tiire conditions; for

example. say. 250 F., somewhat-smaller amounts areefi'ective. adefiniteeffect being. 'obtainedwitl'i as..little.as.,0;02 .Among otherthings; the. aide hyde acts on theproteinpflthefiourto harden it;

It .istk'nown that .if.'starches are roasted" long' enough. at highv.enough. tem eratures; sayiar'o'und- 3.009. F. orperhapssomewhat-higher; the starches' will besuiiiciently. degraded. to form,dextrin'es or other. starch.-modification products. One. of the objectsof this. invention, however, is; to" provide a. flourprodiict in which.the starchylpoi'tion thereof. is. substantially unmodified] orunconverted; and thereforelit, is desirable in f the prac tice of theinvention to avoid such excessiveh'eao ins: of. the. product that would?cause (the; starch component. of the flour. to be substantiallymodified. or converted.

For the purposes of. 'th'is;invention'it' is de= sirable that the flourbe treatedwithformalde hyde under substantially.s'drwconditions. By theterm substantially dry conditions I wish to distinguish between mytr-eatment of the flour in a*powderefpuNerulnt form rather than in*- theform of a dough-or ash-irryz -It shouldbe"un'der-'-- stood; however,"that normal amounts-oimoisthe flour in order to obtain a product havingthe characteristics previously mentioned will, as previously indicated,vary somewhat depending upon the proportion of formaldehyde and thetemperature used. Thus, at ordinary temperatures an appreciable effectis obtained in one day (24 hours) but about 7 days (168 hours) isusually required to obtain the maximum effect; onthe other hand, at atemperature of 250 F. the

result can be accomplished by roasting an intimate blend of theparaformaldehyde and flour for 1 to 1 /2 hours or for a longer period,say 6 hours, if desired. The flour and formaldehyde compound are coactedfor a period sufficiently long to produce a product which formsdispersions in water substantially without lumping or forming dough, ascontrasted with the original untreated fiour which readily lumps, ballsor forms a dough when attempts are made to disperse it. Thesedispersions of the new products herein produced, moreover, exhibitreduced foaming characteristics, as compared with the original untreatedfiour. The roasting may be [carried out at higher temperatures, belowthose at which charring occurs, for shorter periods of time which arepreferably insufficiently long to bring about substantial modificationof the starchy content of the fiour.

Flours naturally having a pH around 6.0 to 6.5, especially wheat floursand rye flours, are well suited to the practice of the invention. Thepresence of too much acidity during the reaction of the flour with theformaldehyde compound is tobe avoided because under substantially acidconditions formaldehyde will react with the starch'component of theflour and tend to render it less capable of being completely gelatinizedwhen cooked with water. For the purposes of my invention this conditionis undesirable. I have found that by keeping the pH of the flour mixtureabove 5.0 the action of the formaldehyde is confined to the proteincomponent of the flour and the starch component is not appreciablyaffected. A preferred pH is from about 6 to about 9.

The products produced in accordance with the invention are inpulverulent or powder formand are readily dispersible in water to formthin slurries with say 4 parts of water per part of flour product. Theymay be gelatinized in water by heating in the usual manner and do notfoam excessively when agitated or beaten in the presence of water, nordo they tend to thin out. Furthermore, they are stable in both the solidand dispersed forms.

The invention will be further understood but is not limited by thefollowing examples in which the proportions are given in parts by weightunless otherwise indicated:

Example I 100 parts of white rye flour was blended at 75 F. with 0.3% ofparaformaldehyde and the blend was allowed to stand for 7 days.

At the end ofthat time the pulverulent product was found to be readilydispersible in water to form a thin slurry with 4 parts of water perpart of the product by weight. This product was found to be useful as acorrugating adhesive, as a beater size in paper making, as a'rug anchorsize, and as a practical substitute for starch in many applicationswhere starch has heretofore been used and where flour could not be usedsatisfactorily.

Example II I 100 parts of white rye flour was intimately blended with0.1% of paraformaldehyde and the blend was roasted at 250 F. for 1 to 1/2 hours. The product obtained was found to be very readily dispersiblein water to form thin slurries with 4 parts of water per part of theproduct. Dispersions of the product in water did not foam excessivelywhen used as a heater size in paper making, nor did the product tend toform balls or dough when dispersed in water. It was relatively stable inthe powder or solid form and likewise when dispersed in water formedrelatively stable dispersions which did not tend to thin out excessivelyon standing. This product also was found to be useful as a corrugatingadhesive, as a size in the manufacture of paper, textiles, rug anchor,and as a practical general substitute for starch.

Example III those described with respect to the product of Example II.

- Example IV A mixture of 9 parts corn starch and 1 part soda ash wasmoistened with 1 part of a 37% solution of formaldehyde. This resultantmixture was thoroughly blended with parts of rye fiour and" allowed tostand for 7 days at a tem- .perature of about 75 F. At the end of thattime the pulverulent product was much more readily dispersible in waterand its tendency to foam on being agitated was greatly reduced ascompared to the original flour.

It was similar in characteristics to those products of the previousexample and is suitable for the same usages.

It will be understood that the various products may differ somewhat in.their characteristics, depending upon Whether they are formed with orwithout heating and also upon the particular type of flour used. Thebest results in the practice of the invention have been obtained by theuse of rye flour. White rye flour, which is the flour obtained fromtheinterior of the rye berry, is preferred, although other grades may beused. The darker grades are undesirable, however, formost purposes.Wheat flour, preferably the first and second clear grades, may beemployed instead of rye flour in the examples given. The invention canalso be applied invt'he manufacture of new and improved flour productsfrom other types of flours containing asubstantial amount of protein orgluten and especially those types which also contain a relatively largeamount of starch. However, for practical purgelatinizable when heatedwith water at temperatures: above the gelatinization temperatures of-thestarchyportions thereof, i. e.,*the starch granules are burst,-as'distinguishedfrom certain pure starch products'heretofore knownand madeby treating starches with acids and formaldehyde. These latter products,although varying somewhat in their properties, tendto swell in water and'forthe most part the granules-donut burst at ordinary gelatinizationtemperatures.

The products of the invention are capable of wide use wheresubstantially pure starches have heretofore been employed. Sincetheyexist in a pulverulent state they are readily shipped and stored assuch. When used as a beater size, products of the invention may be addeddirectly in their solid or powder form to'the beater, or they maybedispersed in water prior to their addition to the beater. They canlikewise be used in a tub size or other types of paper sizes, in sizingor finishing compositions for textiles and for many different purposesin adhesives. They are especially suited, for example, for use informingthe potentially adhesive inert ungelatinized amylaceous substance of theadhesives described in U. S. Patent No. 2,102,937, and the adhesivesthus prepared are especially suited for the'manuiacture of corrugatedboard as describedinU. S. Patent No.,2,051,025.

The product as made from ryefiour is particularly of value as a beatersize in those types of operations wherein the sizing material is addedin a non-cooked state to the beater or head box of the paper machine,and subsequently becomes cooked or gelatinized in situ when the papersheet is passed over the drying rolls of the machine. The lowgelatinization temperature of the starch component of the product madefrom rye flour is one of the features responsible for its favorableperformance in this type of usage.

The invention has the advantage of providing a flour product which canbe used for many industrial applications in place of starch and which isfree from the disadvantages of ordinary whole flours. Other advantageswill be apparent to those skilled in the art.

Having thus described the invention, what I claim as new and desire tosecure by Letters Patent of the United States is:

1. The product of the reaction of a substantially undegraded rye flourwith 0.02% to 5% of paraformaldehyde under substantially dry conditionsat a pH within the range from about 6 to about 9, said product havingthe property of dispersing in water substantially without lumping orforming a dough to produce dispersions which exhibit reduced foamingcharacteristics as compared with similar dispersions of the originaluntreated flour and which are substantially stable against changes inviscosity on standing, said product also being gelatinizable when heatedin water.

2. A process of treating cereal flour to produce a readily waterdispersible, gelatinizable product which comprises intimately blendingand coacting 0.02% to 5% of a formaldehyde with an undegraded cerealflour containing starchy and protein components under substantially dryconditions at a pH in excess of about 5, and under temperatureconditions insufiiciently high and for a period insufficiently long tobring about substantial modification of the starchy content of the flouruntil the flour is rendered capable of forming dispersions in watersubstantially without lumping or forming a dough, said dispersionsexhibiting reduced foaming: charactefi istics as compared withtheoriginal untreated flour and the: starchy components-thereof I beinggelatinizable upon heating.

3. A process as claimed in claim :2 in" which the formaldehyde isparaformaldehyde.

4. A-process as claimed in claim 2 in which the formaldehyde isintroduced in the 'form' of gaseous formaldehyde.

5-. A process as claimed in claim 2in "which the formaldehydeis-introducedin the formof a pulverulent formaldehyde treated starch.

6. A process of treating flour which-comprises intimately blending andcoactingw0;02% to 5% paraformaldehyde with an unde'graded "cereal flourcontaining-starchy and rotein components under substantially dryconditions at tempera-- turesandfor a-period -of"time' insufficient tosubstantially degrade the starchy portion of the flourat a pH within-therange 'from'about 6 to about-9 until the resultantproduct-forms:dispersions in-water' substa'ntiallywithout lumping orforming dough, which dispersions exhibit reduced foaming characteristicsas compared with the original untreated'flour, the starchy components ofthewresultant product being'rg'elatinizable upon heating in the presenceof Water.

7. A process of preparing new and-improved flour products whichcomprises intimately blending and coacting about 0.02% to 5% ofaformaldehyde with a substantially undegraded cereal flour containingstarchy and protein components, based on the weight of the flour, undersubstantially dry conditions at temperatures within the range of about75 F. to about 250 F. at a pH within the range from about 6 to about 9for a period of time within the range from 1 hour to 168 hourssufliciently long to produce a flour product, the aqueous dispersions ofwhich exhibit reduced foaming characteristics as compared with similardispersions of the original untreated flour and are gelatinizable uponheating.

8. A process as claimed in claim '7 in which the flour is a rye flour.

9. A process as claimed in claim 7 in which the flour is a wheat flour.

10. A process of treating flour which comprises intimately blending andcoacting a substantially undegraded whole cereal flour containingstarchy and protein components and about 0.02 to about 1% ofparaformaldehyde, based on the weight of the flour, under substantiallydry conditions, at a pH from about 6 to about 7, at temperatures withinthe range from about 75 F. to about 250 F. for a period of time fromabout 1 hour to 168 hours sufliciently long to produce a product, theaqueous dispersions of which exhibit reduced foaming characteristics ascompared with similar dispersions of the original untreated flour andare gelatinizable upon heating.

11. A flour product formed by intimately blending 0.02% to 5% by weightof a formaldehyde with an undegraded cereal flour containing starchy andprotein components under substan tially dry conditions at temperaturesand for a period of time insuflicient to substantially degrade thestarchy portion of the fiour at a pH in excess of 5 until the resultantproduct forms dispersions in water substantially without lumping orforming a dough, which dispersions exhibit reduced foamingcharacteristics as compared with the original untreated flour and thestarchy components of which are gelatinizable upon heating.

12. A flour product formed by intimately blending'0.02% to by weight ofparaformaldehyde with an undegraded cereal flour containing starchy andprotein components under substantially dry conditions at temperaturesand for a period or time insuiiicient to substantially degrade thestarchy portion of the flour at a pH from about 6 to about 9 until theresultant product forms dispersions in water substantially withoutlumping or-forming a dough, which dispersions exhibit reduced foamingcharacteristics as compared with the original untreated flour and thestarchy components of which are gelatinizable upon heating.

13. A flour product formed by intimately blending 0.02% to 5% by weightof a formaldehyde with a substantially undegraded cereal flourcontaining starchy and protein components under substantially dryconditions at temperatures within the range of about 75 F. to about 250F. at a pH within the range of about 6 to about 9 for a period of timewithin the range from 1 hour to 168 hours suificiently long to produce aflour product, the aqueous dispersions of which exhibit reduced foamingcharacteristics as compared with similar dispersions of the originaluntreated fiour and are gelatinizable upon heating.

14. A gelatinizable flour product exhibiting reduced foamingcharacteristics as compared with the undegraded whole cereal flour fromwhich it is derived, said product being formed by intimately blendingabout 0.02% to about 1% by weight of paraformaldehyde with asubstantially undegraded whole cereal flour containing the usual starchyand protein components under substantially dry conditions at a pH fromabout 6to about '7 at temperatures within the range from about F. toabout 250 F. for a period of time from about 1 hour to 168 hours,depending upon the temperature used, but in any case sufficiently longto produce a product, the aqueous dispersions of which exhibit reducedfoaming,

characteristics as compared with similar dispersionsof the originaluntreated flour and which are gelatinizable upon heating.

JORDAN -V. BAUER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Classen Apr. 19, 1893

